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Regioselective 1,4-Addition of P(O)-H Species to In SituFormed 1-Benzopyrylium Ion from C3-Substituted 2-Chromene Hemiketals to Construct C3-Functionalized C4-Phosphorylated 4-Chromenes.
J Org Chem
January 2025
Antibiotics Research and Re-evaluation Key Laboratory of Sichuan Province, Sichuan Industrial Institute of Antibiotics, School of Pharmacy, Chengdu University, 2025 Chengluo Avenue, Chengdu 610016, P.R. China.
Herein, we report the first example that P(O)-H species including -phosphonates and -phosphine oxides could participate in a highly regioselective 1,4-addition to in situ generated 1-benzopyrylium ion from C3-substituted 2-chromene hemiketals, which provides a brand-new and effective approach for the synthesis of C4-phosphorylated 4-chromenes with diverse C3-functionality (ketone, ester, sulfonyl, aryl, and alkyl groups). In total, the reaction features the use of inexpensive Zn(ClO)·6HO as a catalyst, low catalyst loading (only 5 mol %), mild reaction conditions (60 °C, 10 min to 24 h), and broad substrate scope (46 examples) as well as good to high yields (>90% yield on average). More importantly, mechanistic experiments demonstrated the essential role of the C3-substituent on 2-chromene hemiketals in stabilizing the in situ generated 1-benzopyrylium ion and the regioselective 1,4-addition control.
View Article and Find Full Text PDFConstruction of a prognostic signature based on T-helper 17 cells differentiation-related genes for predicting survival and tumor microenvironment in head and neck squamous cell carcinoma.
Medicine (Baltimore)
January 2025
Department of Otolaryngology, Hangzhou Red Cross Hospital (Zhejiang Hospital of Integrated Traditional Chinese and Western Medicine), Hangzhou, Zhejiang, China.
T-helper 17 (Th17) cells significantly influence the onset and advancement of malignancies. This study endeavor focused on delineating molecular classifications and developing a prognostic signature grounded in Th17 cell differentiation-related genes (TCDRGs) using machine learning algorithms in head and neck squamous cell carcinoma (HNSCC). A consensus clustering approach was applied to The Cancer Genome Atlas-HNSCC cohort based on TCDRGs, followed by an examination of differential gene expression using the limma package.
View Article and Find Full Text PDFDrop Dynamics during Condensation on Superhydrophobic Surfaces in Vapor Shear Flow.
Langmuir
January 2025
Brigham Young University, Provo, Utah 84602, United States.
Accurate models for predicting drop dynamics, such as maximum drop departure sizes, are crucial for estimating heat transfer rates during condensation on superhydrophobic (SH) surfaces. Previous studies have focused on examining the heat transfer rates for SH surfaces under the influence of gravity or vapor flowing over the surface. This study investigates the impact of surface solid fraction and texture scale on drop mobility in a condensing environment with a humid air flow.
View Article and Find Full Text PDFDevelopment and validation of a radiomics-visual evoked potential nomogram for preoperative prediction of visual outcome after endoscopic craniopharyngioma resection.
J Neurosurg
January 2025
Departments of1Neurosurgery.
Objective: Craniopharyngiomas are rare, benign brain tumors that are primarily treated with surgery. Although the extended endoscopic endonasal approach (EEEA) has evolved as a more reliable surgical alternative and yields better visual outcomes than traditional craniotomy, postoperative visual deterioration remains one of the most common complications, and relevant risk factors are still poorly defined. Hence, identifying risk factors and developing a predictive model for postoperative visual deterioration is indeed necessary.
View Article and Find Full Text PDFRole of Ribosomal Protein bS1 in Orthogonal mRNA Start Codon Selection.
Biochemistry
January 2025
Department of Chemistry, University of California, Berkeley, California 94720, United States.
In many bacteria, the location of the mRNA start codon is determined by a short ribosome binding site sequence that base pairs with the 3'-end of 16S rRNA (rRNA) in the 30S subunit. Many groups have changed these short sequences, termed the Shine-Dalgarno (SD) sequence in the mRNA and the anti-Shine-Dalgarno (ASD) sequence in 16S rRNA, to create "orthogonal" ribosomes to enable the synthesis of orthogonal polymers in the presence of the endogenous translation machinery. However, orthogonal ribosomes are prone to SD-independent translation.
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